Herbicidal substituted 4-amino-5-alkylthio-1,2,4-triazol-3-ones

ABSTRACT

Herbicidal substituted 4-amino-5-alkylthio-1,2,4-triazol-3-ones of the formula ##STR1## in which R 1  represents in each case straight-chain or branched alkyl, alkenyl or alkinyl, each of which has up to 4 carbon atoms, and 
     R 2  represents sec-butyl, tert.-butyl or optionally substituted C 5  -C 10  -alkyl, alkenyl or alkinyl, or piperidyl- or morpholinyl-alkyl, optionally substituted C 3 , C 4 , C 5  and C 7  -cycloalkyl, substituted cyclohexyl, or optionally substituted benzyl, phenethyl, naphthylmethyl or naphthylethyl.

This is a division, of application Ser. No. 504,463, filed Apr. 4, 1990now U.S. Pat. No. 5,021,080.

The invention relates to new substituted4-amino-5-alkylthio-1,2,4-triazol-3-ones, to several processes and newintermediates for their preparation, and to their use as herbicides.

It is known that certain 4-amino-5-alkylthio-1,2,4-triazol-3-ones, suchas, for example,4-amino-5-methylthio-2-cyclohexylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one,4-amino-5-methylthio-2-isopropylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-oneand4-amino-5-methylthio-2-butylamino-carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one,are herbicidally active (cf. Japanese Patent 52-125,168). However, theaction of these known compounds is not satisfactory in all respects.

The new substituted 4-amino-5-alkylthio-1,2,4-triazol-3-ones of thegeneral formula (I) ##STR2## in which R¹ represents in each casestraight-chain or branched alkyl, alkenyl or alkinyl, each of which hasup to 4 carbon atoms, and

R² represents sec.-butyl, tert.-butyl, in each case straight-chain orbranched C₅ -C₁₀ -alkyl, C₅ -C₁₀ -alkenyl or C₅ -C₁₀ -alkinyl, orrepresents straight-chain or branched alkyl, alkenyl or alkinyl, each ofwhich has up to 10 carbon atoms and each of which is substituted byhalogen, cyano, C₃ -C₆ -cycloalkyl, aryloxy having 6 to 10 carbon atoms(in particular phenyl or naphthyl) or C₁ -C₆ -alkoxy, or represents C₁-C₆ -alkyl which is in each case substituted by piperidyl ormorpholinyl, or represents cyclopropyl, cyclobutyl, cyclopentyl orcycloheptyl, each of which is optionally substituted by halogen, arylhaving 6 to 10 carbon atoms (in particular phenyl or naphthyl), C₁ -C₆-alkyl or C₁ -C₄ -halogenoalkyl, or represents cyclohexyl which issubstituted by halogen, C₁ -C₆ -alkyl, C₂ -C₄ -alkenyl or C₁ -C₄-halogenoalkyl, or represents phenyl-C₁ -C₂ -alkyl or naphthyl-C₁ -C₂-alkyl, each of which is optionally substituted in the aromaticcomponent by halogen, C₁ -C₄ -alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₄-alkoxy, C₁ -C₂ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, phenoxy and/or phenyl,

have now been found.

The individual carbon chains in, for example, alkyl, halogenoalkyl oralkenyl, are in each case straight-chain or branched.

Furthermore, it has been found that the new substituted4-amino-5-alkylthio-1,2,4-triazol-3-ones of the general formula (I)##STR3## in which R¹ represents in each case straight-chain or branchedalkyl, alkenyl or alkinyl, each of which has up to 4 carbon atoms, and

R² represents sec.-butyl, tert.-butyl, in each case straight-chain orbranched C₅ -C₁₀ -alkyl, C₅ -C₁₀ -alkenyl or C₅ -C₁₀ -alkinyl, orrepresents straight-chain or branched alkyl, alkenyl or alkinyl, each ofwhich has up to 10 carbon atoms and each of which is substituted byhalogen, cyano, C₃ -C₆ -cycloalkyl, aryloxy having 6 to 10 carbon atoms(in particular phenyl or naphthyl) or C₁ -C₆ -alkoxy, or represents C₁-C₆ -alkyl which is in each case substituted by piperidyl ormorpholinyl, or represents cyclopropyl, cyclobutyl, cyclopentyl orcycloheptyl, each of which is optionally substituted by halogen, arylhaving 6 to 10 carbon atoms (in particular phenyl or naphthyl), C₁ -C₆-alkyl or C₁ -C₄ -halogenoalkyl, or represents cyclohexyl which issubstituted by halogen, C₁ -C₆ -alkyl, C₂ -C₄ -alkenyl or C₁ -C₄-halogenoalkyl, or represents phenyl-C₁ -C₂ -alkyl or naphthyl-C₁ -C₂-alkyl, each of which is optionally substituted in the aromaticcomponent by halogen, C₁ -C₄ -alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₄-alkoxy, C₁ -C₂ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, phenoxy and/or phenyl,

are obtained when

(a) hydrazones of the general formula (II) ##STR4## in which R¹ and R²are as defined above and

R³ and R⁴ independently of one another each represent hydrogen, C₁ -C₆-alkyl, phenyl-C₁ -C₄ -alkyl or phenyl,

are reacted with an acid, if appropriate in the presence of a diluent,or when

b) triazolones of the general formula (III) ##STR5## in which R¹ is asdefined above,

are reacted with isocyanates of the general formula (IV)

    R.sup.2 --N═C═O                                    (IV)

in which

R² is as defined above,

if appropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary, or when

c) oxycarbonyltriazolones of the general formula (V) ##STR6## in whichR¹ is as defined above and

R⁵ represents C₁ -C₆ -alkyl, phenyl or phenyl-C₁ -C₄ -alkyl,

are reacted with amines of the general formula (VI)

    R.sup.2 --NH.sub.2                                         (VI)

in which

R² is as defined above,

if appropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary.

Finally, it has been found that the new substituted4-amino-5-alkylthio-1,2,4-triazol-3-ones of the general formula (I) haveinteresting herbicidal properties.

Surprisingly, the substituted 4-amino-5-alkylthio-1,2,4-triazol-3-onesof the general formula (I) according to the invention show aconsiderably more powerful herbicidal action against problem weeds thanthe known, herbicidally active compounds4-amino-5-methylthio-2-cyclohexylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one,4-amino-5-methylthio-2-isopropylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-oneand4-amino-5-methylthio-2-butylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one,which are substances of a similar structure.

The invention preferably relates to compounds of the formula (I) inwhich

R¹ represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec.-butyl, tert.-butyl, allyl, crotonyl or propargyl and

R² represents sec.-butyl, tert.-butyl, in each case straight-chain orbranched pentyl, hexyl, heptyl, octyl, pentenyl, hexenyl, heptenyl,octenyl, pentinyl, hexinyl, heptinyl or octinyl, or represents methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl,pentyl, isopentyl, sec.-pentyl, tert.-pentyl, allyl, crotonyl orpropargyl, each of which is substituted by fluorine, chlorine, bromine,cyano, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenoxy,methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy ortert.-butoxy, or R² furthermore represents methyl, ethyl, n- orisopropyl, each of which is substituted by piperidinyl or morpholinyl,or represents cyclopropyl, cyclobutyl or cyclopentyl, each of which isoptionally substituted by fluorine, chlorine, bromine, methyl,trifluoromethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butylor tert.-butyl, or represents cyclohexyl which is substituted byfluorine, chlorine, methyl, trifluoromethyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec.-butyl, tert.-butyl or propargyl, R² furthermorerepresents benzyl or phenylethyl, each of which is optionallysubstituted in the aromatic component by fluorine, chlorine, bromine,methyl, ethyl, propyl, isopropyl, trifluoromethyl, methoxy, ethoxy,difluoromethoxy, trifluoromethoxy, methylthio, methylsulphinyl,methylsulphonyl, phenoxy and/or phenyl.

In particular, the invention relates to compounds of the formula (I) inwhich

R¹ represents methyl, ethyl, n-propyl, isopropyl or allyl,

R² represents sec.-butyl, tert.-butyl, in each case straight-chain orbranched pentyl, hexyl, heptyl, pentenyl, hexenyl, heptenyl, pentinyl,hexinyl or heptinyl, or represents methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec.-butyl or tert.-butyl, each of which is substitutedby fluorine, chlorine, methoxy, phenoxy or cyano, or representscyclopropyl, cyclobutyl or cyclopentyl, each of which is optionallysubstituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec.-butyl or tert.-butyl, orrepresents cyclohexyl which is substituted by chlorine, methyl,trifluoromethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butylor tert.-butyl, or represents (R/S)-, (R)- or (S)-1-phenylethyl which isoptionally substituted in the aromatic component by fluorine, chlorine,bromine, methyl, ethyl, methoxy, ethoxy, ethoxy and/or phenyl.

If, for example,4-isopropylidenimino-5-ethylthio-2-tert.-butylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-oneis used as the starting compound, the course of the reaction of process(a) according to the invention may be represented by the followingequation: ##STR7##

If, for example, 4-amino-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-oneand tert.-butyl isocyanate are used as the starting substances, thecourse of the reaction of process (b) according to the invention may berepresented by the following equation: ##STR8##

If, for example,4-amino-5-ethylthio-2-methoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-oneand 2-cyanoethylamine are used as the starting substances, the course ofthe reaction of process (c) according to the invention may berepresented by the following equation: ##STR9##

Formula (II) provides a general definition of the hydrazones to be usedas starting substances in process (a) according to the invention for thepreparation of compounds of the formula (I).

In formula (II), R¹ and R² preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or particularly preferred, for R¹ and R² ;

R³ and R⁴, in each case independently of one another, preferablyrepresent hydrogen, straight-chain or branched alkyl having 1 to 4carbon atoms, or phenyl or benzyl, in particular hydrogen, methyl,ethyl, phenyl or benzyl.

The hydrazones of the formula (II) were hitherto unknown. They arelikewise the subject-matter of the present invention. However, they areobtained in analogy to known processes (cf., for example, Acta Pol.Pharm. 38, 153-162 [1981] or C.A. 95: 203841j), for example whentriazolones of the formula (III) ##STR10## in which R¹ is as definedabove,

are reacted with aldehyde or ketones of the formula (VII) ##STR11## inwhich R³ and R⁴ are as defined above,

if appropriate in the presence of a diluent, such as, for example,dichloromethane or toluene, and, if appropriate, in the presence of acatalyst, such as, for example, p-toluene sulphonic acid, attemperatures between 40° C. and 120° C., and the resulting triazolonehydrazones of the formula (VIII) ##STR12## in which R¹, R³ and R⁴ are asdefined above,

are either reacted, in a subsequent second step, with isocyanates of theformula (IV),

    R.sup.2 --N═C═O                                    (IV)

in which

R² is as defined above,

if appropriate in the presence of a diluent, such as, for example,dichloromethane or dioxane, and, if appropriate, in the presence of areaction auxiliary, such as, for example, triethylamine, at temperaturesbetween 20° C. and 150° C.; or, alternatively, in a subsequent secondstep, with chloroformic acid esters of the formula (IX), ##STR13## inwhich R⁵ is as defined above,

if appropriate in the presence of a diluent, such as, for example,tetrahydrofuran, and, if appropriate, in the presence of a reactionauxiliary, such as, for example, sodium hydride or potassiumtert.-butoxide, at temperatures between -20° C. and +40° C., and theresulting triazolones of the formula (X) ##STR14## in which R¹, R³, R⁴and R⁵ are as defined above,

are reacted, in a subsequent third step, with amines of the formula (VI)

    R.sup.2 --NH.sub.2                                         (VI)

in which

R² is as defined above,

is appropriate in the presence of a diluent, such as, for example,tetrahydrofuran or dioxane, and, if appropirate, in the presence of abase, such as, for example, sodium hydroxide or potassium hydroxide, attemperatures between 20° C. and 100° C.

In doing this, it is also possible and may be advantageous to react thetriazolone hydrazones of the formula (VIII) with chloroformic acidesters of the formula (IX) and to subsequently react the resultingtriazolones (X) with amines of the formula (VI) in a so-called one-potprocess.

The triazolones of the formula (III) are known or can be obtained inanalogy to known processes (cf., for example, Japanese Patent52-125,168).

The aldehydes or ketones of the formula (VII), the isocyanates of theformula (IV), the chloroformic acid esters of the formula (IX) and theamines of the formula (VI) are mostly known chemicals for organicsynthesis.

The trizolone hydrazones of the formula (VIII) and the triazolones ofthe formula (X) were hitherto unknown from the literature and form thesubject-matter of the present patent application.

In the formulae (VIII) and (X), R¹, R³ and R⁴ preferably, or inparticular, have the meaning which has been mentioned above inconnection with the description of the compounds of the formulae (I) and(II) according to the invention as being preferred, or particularlypreferred, for R¹, R³ and R⁴. R⁵ preferably represents methyl, ethyl,propyl, isopropyl, butyl, isobutyl, secbutyl, tert-butyl, phenyl orbenzyl.

Formula (III) provides a general definition of the triazolones to beused as starting substances in process (b) according to the inventionfor the preparation of compounds of the formula (I).

In formula (III), R¹ preferably, or in particular, has the meaning whichhas already been mentioned above in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, or particularly preferred, for R¹.

The triazolones of the formula (III) are known or can be obtained inanalogy to known processes (cf., for example, Japanese Patent52-125,168).

Formula (IV) provides a general definition of the isocyanatesfurthermore required as the starting substances for carrying out process(b) according to the invention. In this formula (IV), R² preferablyrepresents those radicals which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred for R².

The isocyanates of the formula (IV) are mostly known chemicals fororganic synthesis.

Formula (V) provides a general definition of the oxycarbonyltriazolonesto be used as substances in process (c) according to the invention forthe preparation of compounds of the formula (I).

In formula (V), R¹ and R⁵ preferably, or in particular, have thosemeanings which have already been mentioned above in connection with thedescription of the compounds of the formulae (I) and (VIII) according tothe invention as being preferred, or particularly preferred, for R¹, andas preferred for R⁵.

The oxycarbonyltriazolones of the formula (V) were hitherto unknown fromthe literature and form the subject-matter of the present patentapplication.

The new compounds of the formula (V) are obtained when triazolones ofthe formula (III) ##STR15## in which R¹ is as defined above,

are reacted with chloroformic acid esters of the formula (IX) ##STR16##in which R⁵ has the abovementioned meaning,

if appropriate in the presence of a diluent, such as, for example,tetrahydrofuran, and, if appropriate, in the presence of a reactionauxiliary, such as, for example, potassium tert-butoxide or sodiumhydride, at temperatures between -20° C. and +100° C.

Other new compounds which form the subject-matter of the presentinvention are 2-chloro-1-methyl-2,3,3-trifluoro-cyclobut-1-yl isocyanateof the formula (IVa), ##STR17## and2-chloro-1-methyl-2,3,3-trifluoro-cyclobut-1-ylamine, of the formula(VIa) ##STR18## which can be employed as intermediates for thepreparation of corresponding compounds of the formula (I).

The new compound of the formula (IVa) is obtained when2-chloro-1-methyl-2,3,3-trifluoro-cyclobutane-1-carboxylic acidchloride, of the formula (X), ##STR19## is reacted with trimethylsilylazide, preferably in the presence of an inert diluent, such as, forexample, toluene, at temperatures between 60° C. and 80° C., and theproduct is isolated by distillation in vacuo.

The compound of the formula (IVa) can also be prepared from the compoundof the formula (VIa) by customary methods, for example by phosgenation.

The new compound of the formula (X) which also forms subject matter ofthe present application is obtained when2-chloro-1-methyl-2,3,3-trifluoro-cyclobutane-2-carboxylic acid, of theformula (XI), ##STR20## is reacted with an acid chloride which issuitable for chlorination, such as, for example, thionyl chloride orphthalic acid dichloride, at temperatures between 0° C. and 100° C., andthe product is isolated by distillation in vacuo.

The new compound of the formula (XI) which also forms subject matter ofthe present application is obtained when2-chloro-1-methyl-2,3,3-trifluoro-cyclobutane-1-carboxylic acid estersof the formula (XII) ##STR21## in which R represents lower alkyl,preferably C₁ -C₄ -alkyl, especially methyl or ethyl, are reacted withan aqueous solution of an alkali metal hydroxide, such as, for example,with aqueous sodium hydroxide solution, at temperatures between 50° C.and 100° C., the mixture is then acidified with a strong acid, such as,for example, hydrochloric acid, and then extracted with an organicsolvent which is virtually immiscible with water, such as, for example,methylene chloride, and the product is isolated from the organic phaseby distillation in vacuo.

The new compounds of the formula (XII) which also form subject matter ofthe present application are obtained when methacrylic acid esters of theformula (XIII) ##STR22## in which R represents lower alkyl, preferablyC₁ -C₄ -alkyl, especially methyl or ethyl, are heated together withchlorotrifluoroethene in an autoclave, preferably in the presence of astabilizer, such as, for example, hydroquinone, at temperatures between50° C. and 150° C., and the product is subsequently isolated bydistillation in vacuo.

The new starting compound of the formula (VIa) ##STR23## is obtainedwhen 2-chloro-1-methyl-2,3,3-trifluoro-cyclobutane-1-carboxamide of theformula (XIV), ##STR24## is reacted with sodium hypochlorite in water attemperatures between 0° C. and 20° C., the mixture is subsequentlytreated with a strong base, such as, for example, sodium hydroxide, andheated to a temperature of between 60° C. and 100° C., and, finally, themixture is preliminarily purified by steam distillation. The oily steamdistillation product can be purified further by distillation in vacuo.

2-Chloro-1-methyl-2,3,3-trifluoro-cyclobutane-1-carboxamide of theformula (XIV) and required as intermediate, was hitherto unknown fromthe literature and forms the subject-matter of the present invention.

The new compound of the formula (XIV) is obtained when2-chloro-1-methyl-2,3,3-trifluoro-cyclobutane-1-carboxylic acid estersof the formula (XII) ##STR25## are reacted with ammonia in an autoclaveat temperatures between 20° C. and 80° C., if appropriate in thepresence of a diluent, such as, for example, methanol, and, ifappropriate, in the presence of a reaction auxiliary, such as, forexample, sodium methoxide, the mixture is subsequently acidified withice-cooling and extracted with an organic solvent which is virtuallyimmiscible with water, such as, for example, methylene chloride, and theproduct is isolated from the organic phase by distillation in vacuo.

The new compounds of the formula (IVa), (VIa), (XIV), (X), (XI) and(XII) are all embraced by the generic formula (XV) ##STR26## in which Zrepresents N═C═O, NH₂, CO--NH₂, CO--Cl, COOH or COOR, where R is loweralkyl.

Acids which are suitable for carrying out process (a) according to theinvention are all inorganic and organic acids which can customarily beused for hydrazone cleavages. Inorganic mineral acids, such ashydrochloric acid, sulphuric acid or phosphoric acid, are preferablyused.

Suitable diluents for carrying out process (a) according to theinvention are all customary organic or inorganic solvents. Diluentswhich are preferably used are polar, water-miscible, organic solvents,in particular alcohols, such as methanol, ethanol, propanol or butanol,their mixtures with water, or pure water.

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 20° C. and 150° C.,preferably at temperatures between 50° C. and 120° C.

Process (a) according to the invention is customarily carried out underatmospheric pressure or under reduced pressure. If the process iscarried out under reduced pressure, the pressure ranges which aresuitable are those between 20 and 400 mbar, preferably between 100 and200 mbar.

For carrying out process (a) according to the invention, 0.01 to 50moles, preferably 0.01 to 20 moles, of acid are generally employed permole of hydrazone of the formula (II). For this purpose, the hydrazoneof the formula (II) is dissolved in a suitable amount of diluent, thenecessary amount of acid is then added, and the mixture is slowlyconcentrated under reduced pressure in the course of several hours.

In a particular embodiment, it is also possible to carry out process (a)according to the invention and to prepare the precursors of the formula(II) required for this purpose, in one reaction step, in a so-calledone-pot process.

In doing this, one possibility is to choose the triazolones of theformula (X) as the starting compounds and to react them in succession ina one-pot process with amines of the formula (VI) and then with acid,according to process (a) according to the invention, or to choose thetriazolone hydrazones of the formula (VIII) as the starting compoundsand to react these in succession in a one-pot process with chloroformicacid esters of the formula (IX), then with amines of the formula (VI)and then with acid, according to process (a) according to the invention,or to choose the triazolones of the formula (III) as the startingcompounds and to react these in succession in a one-pot process withaldehydes or ketones of the formula (VII), then with isocyanates of theformula (IV) and subsequently with acid, according to process (a)according to the invention.

Diluents for carrying out process (b) according to the invention areinert organic solvents. These include, in particular, aliphatic,alicyclic or aromatic, optionally halogenated hydrocarbons, such as, forexample, benzine, benzene, toluene, xylene, chlorobenzene, petroleumether, hexane, cyclohexane, dichloromethane, chloroform and carbontetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran,ethylene glycol dimethyl ether or ethylene glycol diethyl ether,nitriles, such as acetonitrile or propionitrile, amides, such asdimethylformamide, dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide, or esters, such asethyl acetate.

If appropriate, process (b) according to the invention is carried out inthe presence of a suitable reaction auxiliary. Suitable reactionauxiliaries are all customary inorganic or organic bases. These include,for example, tertiary amines, such as triethyl amine,N,N-dimethylaniline, N,N-diethylbenzylamine, N,N-dimethylcyclohexylamineor dibutyltin dilaurate, pyridine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicylononene (DBN) ordiazabicyloundecene (DBU).

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 150° C.,preferably at temperatures between 20° C. and 100° C.

For carrying out process (b) according to the invention, 1.0 to 2.0moles, preferably 1.0 to 1.5 moles, of isocyanate of the formula (IV)and, if appropriate, 0.001 to 2.0 moles, preferably 0.001 to 1.0 mole,of reaction auxiliary are generally employed per mole of triazolone ofthe formula (III).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods.

Suitable diluents for carrying out process (c) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons,such as, for example, benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform andcarbon tetrachloride, ethers, such as diethyl ether, dioxane,tetrahydrofuran, ethylene glycol dimethyl ether or ethylene glycoldiethyl ether, nitriles, such as acetonitrile or propionitrile, amides,such as dimethylformamide, dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide, or esters, such asethyl acetate, or sulphoxides, such as dimethyl sulphoxide.

If appropriate, process (c) according to the invention can be carriedout in the presence of a suitable reaction auxiliary. Suitable reactionauxiliaries are all customary inorganic or organic bases. These include,for example, alkali metal hydroxides, such as sodium hydroxide orpotassium hydroxide, alkali metal carbonates, such as sodium carbonate,potassium carbonate or sodium hydrogen carbonate, and also tertiaryamines, such as triethyl amine, N,N-dimethylaniline, pyridine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicylononene(DBN) or diazabicyloundecene (DBU).

When carrying out process (c) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 120° C.,preferably at temperatures between 20° C. and 50° C.

For carrying out process (c) according to the invention, 1.0 to 5.0moles, preferably 1.0 to 2.5 moles, of amine of the formula (VI) and, ifappropriate, 1.0 to 2.5 moles, preferably 1.0 to 1.2 moles, of reactionauxiliary are generally employed per mole of oxycarbonyltriazolone ofthe formula (V).

The reaction is carried out and the reaction products are worked andisolated by generally customary methods.

In a particular embodiment, it is also possible to carry out process (c)according to the invention and to prepare the precursors of the foumula(V) required for this purpose, in one reaction step, in a so-calledone-pot process.

This process uses triazolones of the formula (III) as startingmaterials, which are reacted in succession in a one-pot process,initially with chloroformic acid esters of the formula (IX) andsubsequently with amines of the formula (VI), according to process (c)according to the invention.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weedkillers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example forests, decorative tree plantings, orchards,vineyards, citrus groves, nut orchards, banana plantations, coffeeplantations, tea plantations, rubber plantations, oil palm plantations,cocoa plantations, soft fruit plantings and hopfields, and for theselective combating of weeds in annual cultures.

The compounds of the formula (I) according to the invention are alsosuitable for selectively combating monocotyledon and dicotyledon weedsin monocotyledon and dicotyledon cultures, both using the pre-emergenceand the post-emergence methods.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene, oralkylnaphthalenes, chlorinated aromatic and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates, assolid carriers for granules there are suitable: for example crushed andfractionated natural minerals such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

For combating weeds, the active compounds according to the invention, assuch or in the form of their formulations, can also be used as mixtureswith known herbicides, finished formulations or tank mixes beingpossible.

Suitable herbicides for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethylurea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans. Mixtures with2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butyricacid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP);5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-benzoic acid(ACIFLUORFEN); 2-chloro-2',6'-diethyl-N-methoxy-methylacetanilide(ALACHLOR);methyl-6,6-dimethyl-2,4-dioxo-3-[1-(2-propenyloxyamino)-butylidene]-cyclohexanecarboxylicacid (ALLOXYDIM); 2-chloro-4-ethylamino-6-isopropylamino1,3,5-triazine(ATRAZINE); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide(BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX);3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL);N-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)-acetamide (BUTACHLOR);ethyl2-{[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]aminosulphonyl}-benzoate(CHLORIMURON);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea(CHLORTOLURON);exo-1-methyl-4-(1-methylethyl)-2-(2-methylphenyl-methoxy)-7-oxabicyclo-(2,2,1)-heptane(CINMETHYLIN); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID);2-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine (CYANAZINE);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester orits ethyl ester (DICLOFOP); S-ethyl N,N-di-n-propyl-thiocarbamidate(EPTAME); 4-amino-6-t-butyl3-ethylthio-1,2,4-triazin-5(4H)-one(ETHIOZIN); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoicacid, its methyl ester or its ethyl ester (FENOXAPROP);2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or itsbutyl ester (FLUAZIFOP);[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its1-methylheptyl ester (FLUROXYPYR);5-(2-chloro-4-trifluoromethylphenoxy)-N-methylsulphonyl-2-nitrobenzamide(FOMESAFEN);2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]phenoxy}-propanoicacid or its ethyl ester (HALOXYFOP);2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolincarboxylicacid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETHAPYR);3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL);N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON);(2-ethoxy-1-methyl-2-oxo-ethyl)5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrobenzoate (LACTOFEN);(2-methyl-4-chlorophenoxy)acetic acid (MCPA);(4-chloro-2-methylphenoxy)-propionic acid (MCPP);N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET);2-chloro-N-(2,6-dimethylphenyl)-N-[(1H)-pyrazol-1-yl-methyl]-acetamide(METAZACHLOR);2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide(METOLACHLOR);2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}benzoicacid or its methyl ester (METSULFURON); S-ethylN,N-hexamethylenethiocarbamate (MOLINATE);4-(di-n-propylamino)-3,5-dinitrobenzenesulphonamide (ORYZALIN);2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitro-phenyl ether(OXYFLUORFEN); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline(PENDIMETHALIN); O-(6-chloro-3-phenylpyridazin-4-yl) S-octylthiocarbonate (PYRIDATE);2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione(SETHOXYDIM); 2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine (SIMAZINE);2,4-bis-[N-ethylamino]-6-methylthio-1,3,5-triazine (SIMETRYNE);4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate(THIAMETURON); S-[(4-chlorophenyl)-methyl]-N,N-diethylthiocarbamate(THIOBENCARB); N,N-diisopropyl S-(2,3,3-trichloroallyl) thiocarbamate(TRIALLATE); 2,6-dinitro4-trifluoromethyl-N,N-dipropylaniline(TRIFLURALIN) and ethyl2-[4-(6-chloro-2-quinoxalinyloxy)-phenoxy]propionate (QUIZALOFOP) arealso possible. Surprisingly, some mixtures also show a synergisticaction.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 10 kg of active compound perhectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR27##

Process (a)-one-pot variant

A mixture of 7.3 g (0.05 mol) of4-amino-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, a spatula-tipfull of p-toluenesulphonic acid and 100 ml of acetone is refluxed for 3hours. After the mixture has been concentrated, the residue is taken upin 50 ml of acetonitrile, 5.5 g (0.055 mol) of tert-butyl isocyanate and0.1 g of diazabicycloundecene (DBU) are added, and the mixture is thenstirred for 12 hours at 20° C.

After the mixture has been reconcentrated, the residue which remains istaken up in 100 ml of ethanol/water (1:1), 5 ml of concentratedhydrochloric acid are added, and the mixture is then evaporated todryness at 60° C. and under slightly subatmospheric pressure, within 3hours. The residue is taken up in methylene chloride, the mixture iswashed with water until neutral, dried using sodium sulphate andfiltered. The solvent is removed from the filtrate by distillation in awater pump vacuum, and the product which remains in the residue isbrought to crystallization by trituration with diethyl ether. This gives6.0 g (49% of theory) of4-amino-5-methylthio-2-tert-butylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 134° C.

EXAMPLE 2 ##STR28##

Process (b)

7.3 g (0.05 mol) of4-amino-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, are suspendedin 100 ml of acetonitrile, 1 g of diazabicycloundecene (DBU) and 6.0 g(0.05 mol) of 2-chloro-1-methyl-ethyl isocyanate are added to thesuspension with stirring, and the mixture is stirred for 12 hours at 20°C.

It is then concentrated, the residue is taken up in methylene chloride,the mixture is washed to neutrality, dried using sodium sulphate andfiltered. The solvent is removed from the filtrate by distillation undera water pump vacuum, and the product which remains in the residue isbrought to crystallization by trituration with diethyl ether. This gives6.0 g (45% of theory) of4-amino-5-methylthio-2-(2-chloro-1-methylethylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 136° C.

The compounds of the formula (I) ##STR29## listed in Table 1 below canbe prepared analogously to Examples 1 and 2 and following the generaldescription of the preparation processes according to the invention.

                                      TABLE 1                                     __________________________________________________________________________    Examples of the compounds of the formula I                                    Example                       Melting                                         No.  R.sup.1 R.sup.2          point (°C.)                              __________________________________________________________________________     3   CH.sub.3                                                                               ##STR30##       110                                              4   CH.sub.3                                                                              C(CH.sub.3).sub.2 CCH                                                                          178                                              5   CH.sub.3                                                                              C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  125                                              6   CH.sub.3                                                                              C(CH.sub.3).sub.2 (CH.sub.2).sub.3 CH.sub.3                                                     95                                              7   CH.sub.3                                                                               ##STR31##       124                                              8   CH.sub.3                                                                              C(CH.sub.3).sub.2 CHCl.sub.2                                                                   172                                              9   CH.sub.3                                                                               ##STR32##       141                                             10   CH.sub.3                                                                              C(CH.sub.3).sub.2 CH.sub.2 F                                                                   152                                             11   CH.sub.3                                                                              C(CH.sub.3).sub.2 CN                                                                           153                                             12   C.sub.2 H.sub.5                                                                       C(CH.sub.3).sub.3                                                13   C.sub.2 H.sub.5                                                                       C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                  101                                             14   C.sub.2 H.sub.5                                                                       C(CH.sub.3).sub.2 CH.sub.2 F                                     15   CH.sub.3                                                                              CH.sub.2 CF.sub.3                                                16   CH.sub.3                                                                              CH(CH.sub.3)(CF.sub.3)                                           17   CH.sub.3                                                                              CH(C.sub.2 H.sub.5)CH.sub.2 Cl                                   18   CH.sub.3                                                                              CH(CH.sub.3)CHCl(CH.sub.3)                                       19   CH.sub.3                                                                              CH(CH.sub.2 Cl)CHCH.sub.2                                        20   CH.sub.3                                                                              CH(CH.sub.3)CHCCl.sub.2                                          21   CH.sub.3                                                                              C(CH.sub.3)(CH.sub.2 F).sub.2                                    22   CH.sub.3                                                                              C(CH.sub.3).sub.2 CF.sub.3                                       23   CH.sub.3                                                                              CH(CH.sub.3)C.sub.3 H.sub.7 -n                                   24   CH.sub.3                                                                              CH(CH.sub.3)C.sub.3 H.sub.7 -iso                                 25   CH.sub.3                                                                              C(CH.sub.3)(CN)C.sub.3 H.sub.7 -iso                              26   CH.sub.3                                                                              CH(C.sub.2 H.sub.5).sub.2                                        27   CH.sub.3                                                                              C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                28   CH.sub.3                                                                              C(CH.sub.3).sub.2 CHCCl.sub.2                                    29   CH.sub.3                                                                              C.sub.6 H.sub.13 -n                                              30   CH.sub.3                                                                              CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.7 -iso                        31   CH.sub.3                                                                              CH(CH.sub.3)C.sub.4 H.sub.9 -tert.                               32   CH.sub.3                                                                              C(CH.sub.3).sub.2 C.sub.3 H.sub.7 -n                             33   CH.sub.3                                                                              C(CH.sub.3).sub.2 C.sub.3 H.sub.7 -i                             34   CH.sub. 3                                                                             C(CH.sub.3)(C.sub.2 H.sub.5).sub.2                               35   CH.sub.3                                                                              CH(CH.sub.3)C.sub.5 H.sub.11 -n                                  36   CH.sub.3                                                                              CH(CH.sub.3)C.sub.4 H.sub.9 -n                                   37   CH.sub.3                                                                              CH(CH.sub.3)CH.sub.2 CH.sub.2 C.sub.3 H.sub.7 -iso               38   CH.sub.3                                                                              CH(CH.sub.3)CH.sub.2 C.sub.4 H.sub.9 -tert.                      39   CH.sub.3                                                                              C(CH.sub.3).sub.2 CH(CH.sub.3)CHCCl.sub.2                        40   CH.sub.3                                                                              C(C.sub.2 H.sub.5).sub.3                                         41   CH.sub.3                                                                              CH(CH.sub.3)C.sub.6 H.sub.13 -n                                  42   CH.sub.3                                                                              C(CH.sub.3).sub.2 CH.sub.2 C.sub.4 H.sub.9 -t                    43   CH.sub.3                                                                              CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.3 H.sub.7 -iso                44   CH.sub.3                                                                               ##STR33##                                                       45   CH.sub.3                                                                               ##STR34##                                                       46   CH.sub.3                                                                               ##STR35##                                                       47   CH.sub.3                                                                               ##STR36##                                                       48   CH.sub.3                                                                               ##STR37##       140                                             49   CH.sub.3                                                                               ##STR38##                                                       50   CH.sub.3                                                                               ##STR39##                                                       51   CH.sub.3                                                                               ##STR40##                                                       52   CH.sub.3                                                                               ##STR41##                                                       53   CH.sub.3                                                                               ##STR42##                                                       54   CH.sub.3                                                                               ##STR43##                                                       55   CH.sub.3                                                                               ##STR44##                                                       56   CH.sub.3                                                                               ##STR45##                                                       57   CH.sub.3                                                                               ##STR46##                                                       58   CH.sub.3                                                                               ##STR47##                                                       59   CH.sub.3                                                                               ##STR48##                                                       60   CH.sub.3                                                                               ##STR49##                                                       61   CH.sub.3                                                                               ##STR50##                                                       62   CH.sub.3                                                                               ##STR51##                                                       63   CH.sub.3                                                                               ##STR52##                                                       64   CH.sub.3                                                                              CH(CH.sub.3)CH.sub.2 OCH.sub.3                                   65   CH.sub.3                                                                              CH(CH.sub.3)CH.sub.2 OC.sub.6 H.sub.5                            66   CH.sub.3                                                                               ##STR53##                                                       67   CH.sub.3                                                                               ##STR54##       171                                             68   CH.sub.3                                                                               ##STR55##       230                                             69   CH.sub.3                                                                               ##STR56##       147                                             70   CH.sub.3                                                                               ##STR57##       132                                             71   CH.sub.3                                                                               ##STR58##       105                                             72   CH.sub.3                                                                               ##STR59##       122                                             73   CH.sub.3                                                                               ##STR60##       117                                             74   CH.sub.3                                                                               ##STR61##       127                                             75   CH.sub.3                                                                               ##STR62##       167                                             76   n-C.sub.3 H.sub.7                                                                     C(CH.sub.3).sub.2 CH.sub.2 Cl                                    77   CH.sub.3                                                                               ##STR63##       102                                             78   CH.sub.2 CHCH.sub.2                                                                   C(CH.sub.3).sub.2 CH.sub.2 Cl                                                                   97                                             79   CH.sub.3                                                                              (CH.sub.2).sub.2 OC.sub.2 H.sub.5                                                              163                                             __________________________________________________________________________

For example, the compound listed in Table 1 as Example 70 can beprepared as described below: ##STR64##

Process (c)

A mixture of 12.6 g (0.05 mol) of4-amino-5-methylthio-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one,9.5 g (0.05 mol) of 1-(3,4-dichlorophenyl)-ethylamine and 100 ml oftetrahydrofuran is stirred for 16 hours at 20° C. and subsequentlyconcentrated. The residue is triturated with ethyl acetate, and theproduct obtained in the form of crystals is isolated by filtering offwith suction.

This gives 2.9 g (16% of theory) of4-amino-5-methylthio-2-(1-(3,4-dichloro-phenyl)-ethylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 132° C.

STARTING SUBSTANCES OF THE FORMULA (V) Example (V-1) ##STR65##

170 g (1.5 mol) of potassium tert.-butoxide is added in portions to amixture of 201 g (1.40 mol) of4-amino-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one and 1000 ml oftetrahydrofuran at 0° C. The reaction mixture is stirred for a furtherhour at 0° C. 214 g (1.4 mol) of phenyl chloroformate are subsequentlyadded dropwise with stirring at 0° C. The reaction solution is stirredat 20° C. for a further 15 hours and concentrated on a rotaryevaporator. 300 ml of water and 500 ml of methylene chloride are addedto the residue. A colorless solid precipitates on the phase boundary andis isolated by filtration with suction.

This gives 218 g (63% of theory) of4-amino-5-methylthio-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 161° C.

The following is obtained analogously

Example (V-2) ##STR66##

4-amino-5-methylthio-2-benzyloxycarbonyl-2,4-dihydro-3H1,2,4-triazol-3-one.

Example IVa ##STR67##

100 g (0.45 mol) of1-methyl-2-chloro-2,3,3trifluorocyclobutanecarboxylic acid chloride areadded dropwise to a solution of 61.3 g (0.53 mol) of trimethylsilylazide in 250 ml of dry benzene. The mixture is heated to 75° C. andstirred until the evolution of gas has ceased. The solvent issubsequently distilled off, and the product which remains isfractionated.

This gives 77 g (86% of theory) of the above-shown product, boilingpoint: 75°-78° C./80 mm Hg.

Example X ##STR68##

220 g (1.09 mol) of1-methyl-2-chloro-2,3,3-trifluorocyclobutanecarboxylic acid are stirredovernight at room temperature with 250 g (1.23 mol) of phthalic aciddichloride. The acid chloride is subsequently distilled off.

This gives 238 g (99% of theory) of the above-shown product, boilingpoint: 54°-56° C./23 mm Hg.

Example XI ##STR69##

573 g (2.65 mol) of methyl1-methyl-2-chloro-2,3,3-trifluorocyclobutanecarboxylate, 233 g (5.8 mol)of sodium hydroxide and 1000 ml of water are stirred for three hours at80° C. The mixture is acidified using concentrated hydrochloric acid andextracted using dichloromethane, and the organic phases are dried anddistilled. This gives 472 g (88% of theory) of the above-shown product,boiling point: 112°-116° C./16 mm Hg (60% of trans-isomer, 40% ofcis-isomer).

Example XII-1 ##STR70##

750 g (7.5 mol) of methyl methacrylate, 700 g (6.0 mol) ofchlorotrifluoroethene and 3 g of hydroquinone are heated in a steelautoclave for 12 hours at 120° C. The product is fractionated directly.

This gives 780 g (60% of theory) of the above-shown product, boilingpoint: 57°-59° C./14 mm Hg.

Example XIV ##STR71##

400 g (1.8 mol) of methyl1-methyl-2-chloro-2,3,3-trifluorocyclobutanecarboxylate and 62 ml of 30%strength sodium methoxide solution are dissolved in 1500 ml of methanol,and 620 ml of liquid ammonia are added to the mixture in an autoclave.The mixture is stirred for 14 hours at 50° C., poured onto ice, slightlyacidified using hydrochloric acid and extracted using dichloromethane.The combined organic phases are washed with dilute hydrogen carbonatesolution, dried and concentrated. The amide is distilled.

This gives 254 g (68% of theory) of the above-shown product, boilingpoint: 138°-140° C./200 mg Hg.

Example VIa ##STR72##

571 ml of 13% strength sodium hypochlorite solution (=1 mol NaOCl) areadded dropwise at 10° C. to a suspension of 200 g (0.99 mol) of1-methyl-2-chloro-2,3,3-trifluorocyclobutanecarboxamide in 1.2 l ofwater, during which process the amide slowly dissolves. Stirring iscontinued for 1 hour at 10° C., and 400 ml of 50% strength NaOH solutionare added dropwise. The mixture is subsequently heated to 80° C.,stirred at 80° C. for one hour and subjected to steam distillation. Theamine is separated off and fractionated.

This gives 105 g (61% of theory) of the above-shown product, boilingpoint 54°-55° C./48 mm Hg.

Use Examples

In the use examples which follow, the compounds listed below were usedas comparison substances: ##STR73##4-amino-5-methylthio-2-cyclohexylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one##STR74##4-amino-5-methylthio-2-isopropylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one##STR75##4-amino-5-methylthio-2-butylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one(all known from Japanese Patent 52-125,168).

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil, and, after 24 hours,watered with the preparation of active compound. In this context, it isexpedient to keep constant the amount of water per unit area. Theconcentration of active compound in the preparation is of no importance,only the application rate of active compound per unit area beingdecisive. After three weeks, the degree of damage to the plants is ratedin % damage in comparison to the development of the untreated control.The figures denote:

0%=no action (like untreated control)

100%=total destruction

A clearly superior effectiveness compared with the known compounds (A)and (C) is shown in this test, for example, by the compounds ofPreparation Examples (1), (4), (5), (9) and (10).

Example B Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 1,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

A clearly superior effectiveness (combined with good selectivity towardscrop plants) compared with the known compounds (A), (B) and (C) is shownin this test, for example, by the compounds of Preparation Examples (3),(4), (5), (6), (7), (10), (67), (71) and (73).

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswith the spirit and scope of the invention will suggest themselves tothose skilled in the art.

We claim:
 1. A compound of the formula (XV) ##STR76## in which Zrepresents N═C═O, or NH₂.
 2. A compound according to claim 1, in which Zis NH₂.
 3. A compound according to claim 1, in which Z is N═C═O.